EP0809666B2 - Biologisch abbaubare polymere, verfahren zu deren herstellung sowie deren verwendung zur herstellung bioabbaubarer formkörper - Google Patents

Biologisch abbaubare polymere, verfahren zu deren herstellung sowie deren verwendung zur herstellung bioabbaubarer formkörper Download PDF

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EP0809666B2
EP0809666B2 EP96902980A EP96902980A EP0809666B2 EP 0809666 B2 EP0809666 B2 EP 0809666B2 EP 96902980 A EP96902980 A EP 96902980A EP 96902980 A EP96902980 A EP 96902980A EP 0809666 B2 EP0809666 B2 EP 0809666B2
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mol
polyether ester
range
biodegradable
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EP0809666A1 (de
EP0809666B1 (de
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Volker Warzelhan
Gunter Pipper
Ursula Seeliger
Peter Bauer
Dieter Bernhard Beimborn
Motonori Yamamoto
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BASF SE
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BASF SE
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/91—Polymers modified by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/60—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from the reaction of a mixture of hydroxy carboxylic acids, polycarboxylic acids and polyhydroxy compounds
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
    • A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
    • A61L15/22—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons containing macromolecular materials
    • A61L15/26—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
    • A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
    • A61L15/42—Use of materials characterised by their function or physical properties
    • A61L15/62—Compostable, hydrosoluble or hydrodegradable materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C08G63/20—Polyesters having been prepared in the presence of compounds having one reactive group or more than two reactive groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/66—Polyesters containing oxygen in the form of ether groups
    • C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/66—Polyesters containing oxygen in the form of ether groups
    • C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/672—Dicarboxylic acids and dihydroxy compounds
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/40—Bio-organic fraction processing; Production of fertilisers from the organic fraction of waste or refuse

Definitions

  • the present invention relates to biodegradable polyether esters Q2 according to claim 1.
  • the invention further relates to polymers and biologically degradable thermoplastic molding compositions according to subclaims, processes for their manufacture, their use for manufacture biodegradable moldings and adhesives, biodegradable degradable moldings, foams and blends with starch, available from the polymers or molding compositions according to the invention.
  • EP-A 565,235 contains aliphatic copolyesters [-NH-C (O) O -] - groups ("urethane units").
  • the Copolyesters of EP-A 565,235 are made by reacting a prepolyester - obtained by reacting essentially succinic acid and an aliphatic diol - with a diisocyanate, preferably hexamethylene diisocyanate. Implementation with the diisocyanate is required according to EP-A 565,235, because of the polycondensation alone only polymers with such molecular weights can be obtained that are not satisfactory mechanical Have properties.
  • the crucial disadvantage is that Use of succinic acid or its ester derivatives for the production the copolyester because succinic acid or its derivatives expensive and not available on the market in sufficient quantities.
  • succinic acid as the only one Acid component the polyesters made from it only extremely slowly degraded.
  • copolyether esters are predominantly based aromatic dicarboxylic acids, short-chain ether diol segments such as Diethylene glycol, long-chain polyalkylene glycols such as polyethylene glycol (PEG) and aliphatic diols known, at least 85 mol% of the polyester diol residue from a terephthalic acid residue consist.
  • PEG polyethylene glycol
  • aliphatic diols known, at least 85 mol% of the polyester diol residue from a terephthalic acid residue consist.
  • polyesters which are largely aromatic Dicarboxylic acid units and aliphatic diols built such as PET (polyethylene terephthalate) and PBT (polybutylene terephthalate), are not enzymatically degradable. This is also valid for copolyesters and copolyetheresters, the blocks, made up of aromatic dicarboxylic acid units and aliphatic diols or Ether diols.
  • WO 92/09654 discloses aliphatic-aromatic copolyesters which may be biodegradable, and from 95-35 mol% CO-C8 alkyl or C2-C4-oxyalkyldicarboxylic acid residues, 5-65 mol% of C6-C10-aryldicarboxylic acid residues as well as C2-C8-alkyl or -oxyalkyldiol residues are built up.
  • the mechanical properties of these copolyesters are in need of improvement, however.
  • the object of the present invention was therefore, biologically, i.e. using microorganisms to provide degradable polymers, that do not have these disadvantages.
  • the Polymers according to the invention from known and inexpensive monomer units producible and insoluble in water.
  • there Biodegradation should not be caused by microorganisms Cost of the mechanical properties can be achieved to the Do not limit the number of application areas.
  • the polyether esters P1 are characterized by a molecular weight (M n ) in the range from 5000 to 80,000, preferably from 6,000 to 45,000, particularly preferably from 8,000 to 35,000 g / mol, a viscosity number in the range from 30 to 450, preferably from 50 to 400 g / ml (measured in o-dichlorobenzene / phenol (weight ratio 50/50) at a concentration of 0.5% by weight of polyether ester P1 at a temperature of 25 ° C.) and a melting point in the range from 50 to 200, preferably from 60 to 160 ° C, and the further proviso that the polyether esters P1 have both hydroxyl and carboxyl end groups, the molar ratio of carboxyl end groups to hydroxyl end groups being greater than one, preferably greater than two.
  • M n molecular weight in the range from 5000 to 80,000, preferably from 6,000 to 45,000, particularly preferably from 8,000 to 35,000
  • the sulfonate group-containing compound is usually used Alkali or alkaline earth metal salt of a sulfonate group-containing Dicarboxylic acid or its ester-forming derivatives, preferred Alkali metal salts of 5-sulphoisophthalic acid or its Mixtures, particularly preferably the sodium salt.
  • the dihydroxy compounds (a21) used are a compound selected from the group consisting of C 2 -C 6 alkanediols and C 5 -C 10 cycloalkanediols, such as ethylene glycol, 1,2-, 1,3-propanediol, 1,2 -, 1,4-butanediol, 1,5-pentanediol or 1,6-hexanediol, in particular ethylene glycol, 1,3-propanediol and 1,4-butanediol, cyclopentanediol, cyclohexanediol, 1,2-cyclohexanedimethanol, 1,4-cyclohexanedimethanol , particularly preferably ethylene glycol and 1,4-butanediol, and mixtures thereof.
  • C 2 -C 6 alkanediols and C 5 -C 10 cycloalkanediols such as ethylene glyco
  • the molecular weight (M n ) of the polyethylene glycol is generally chosen in the range from 250 to 8000, preferably from 600 to 3000 g / mol.
  • From 0.01 to 4 mol% is used, particularly preferably from 0.05 up to 4 mol%, based on component (a1), at least one Compound D with at least three capable of ester formation Groups.
  • the melt viscosity impact resistance changed as desired increased and the crystallinity of the polymers according to the invention or Molding compounds are reduced.
  • biodegradable polyether esters P1 The production of the biodegradable polyether esters P1 is basically known (Sorensen and Campbell, "Preparative Methods of Polymer Chemistry ", Interscience Publishers, Inc., New York, 1961, pages 111 to 127; Encycl. of polym. Science and Eng., Vol. 12, 2nd Ed., John Wiley & Sons, 1988, pp. 75-117; Plastic manual, volume 3/1, Carl Hanser Verlag, Kunststoff, 1992, pp. 15 to 23 (production of poly parents); WO 92/13020; EP-A 568,593; EP-A 565,235; EP-A 28,687), so that closer No information about this.
  • component (a2) based on component (a1) used, for example up to 2 1/2 times, preferably up to 1.67 times.
  • the biodegradable is produced Polyetherester P1 with the addition of suitable, known per se Catalysts such as metal compounds based on the following Elements such as Ti, Ge, Zn, Fe, Mn, Co, Zr, V, Ir, La, Ce, Li, and Ca, preferably organometallic compounds based on these Metals such as salts of organic acids, alkoxides, acetylacetonates and the like, particularly preferably based on zinc, tin and titanium.
  • suitable, known per se Catalysts such as metal compounds based on the following Elements such as Ti, Ge, Zn, Fe, Mn, Co, Zr, V, Ir, La, Ce, Li, and Ca, preferably organometallic compounds based on these Metals such as salts of organic acids, alkoxides, acetylacetonates and the like, particularly preferably based on zinc, tin and titanium.
  • component (a1) When using dicarboxylic acids or their anhydrides as Component (a1) can be esterified with component (a2), take place simultaneously or after the transesterification.
  • component (a2) For example can the process described in DE-A 23 26 026 for the preparation modified polyalkylene terephthalates can be used.
  • components (a1) and (a2) in the Usually under reduced pressure or in an inert gas stream, for example, from nitrogen, when heated further to a Temperature in the range of 180 to 260 ° C the polycondensation up to the desired molecular weight considering the Molar ratio of the carboxyl end groups to hydroxyl end groups, that you choose greater than one, preferably greater than two, carried out.
  • stabilizers can also be used in this process step (see EP-A 21042 and US-A 4,321,341).
  • Stabilizers are, for example, those in EP-A 13 461, US 4,328,049 or in B. Fortunato et al., Polymer Vol. 35, No. 18, pp. 4006 to 4010, 1994, Butterworth-Heinemann Ltd. Phosphorus compounds. Some of these can also be used as Deactivators of the catalysts described above act. exemplary may be mentioned: organophosphites, phosphonous acid and phosphorous acid.
  • Examples include: trialkyl phosphites, triphenyl phosphite, Trialkyl phosphates, triphenyl phosphate and tocopherol (for example available as Uvinul® 2003AO (BASF)).
  • Copolymers When using the biodegradable according to the invention Copolymers, e.g. in the packaging sector e.g. for food, it is usually desirable to adjust the content chosen catalyst as low as possible and do not use toxic compounds. In contrast to others Heavy metals such as lead, tin, antimony, cadmium, chromium etc. Titanium and zinc compounds are generally not toxic ("Sax Toxic Substance Data Book ", Shizuo Fujiyama, Maruzen, K.K., 360 S. (cited in EP-A 565,235), see also Römpp Chemie Lexikon Vol. 6, Thieme Verlag, Stuttgart, New York, 9th edition, 1992, Pp. 4626 to 4633 and 5136 to 5143). Examples include: Dibutoxydiacetoacetoxytitan, Tetrabutylorthotitanat and Zinc (II) acetate.
  • the weight ratio of catalyst to biodegradable Polyetherester P1 is usually in the range of 0.01: 100 to 3: 100, preferably from 0.05: 100 to 2: 100, with highly active Titanium compounds can also be used in smaller quantities like 0.0001: 100.
  • the catalyst can immediately at the beginning of the reaction shortly before the excess diol or if desired also distributed in several portions during the production of the biodegradable polyether esters P1 be used. If desired, different ones can also be used Catalysts or mixtures thereof are used.
  • the biodegradable polyether esters P2 are characterized by a molecular weight (M n ) in the range from 5000 to 80,000, preferably from 6,000 to 45,000, particularly preferably from 10,000 to 40,000 g / mol, a viscosity number in the range from 30 to 450, preferably from 50 to 400 g / ml (measured in o-dichlorobenzene / phenol (weight ratio 50/50) at a concentration of 0.5% by weight of polyether ester P2 at a temperature of 25 ° C.) and a melting point in the range from 50 to 235, preferably from 60 to 235 ° C, and have both hydroxyl and carboxyl end groups, the molar ratio of carboxyl end groups to hydroxyl end groups being greater than one, preferably greater than two.
  • M n molecular weight
  • biodegradable polyether esters P2 expediently takes place analogously to the preparation of the polyether esters P1, the addition of the hydroxycarboxylic acid B1 both at the beginning of the Implementation as well as after the esterification or transesterification stage can be done.
  • the hydroxycarboxylic acid is used B1 a such as glycolic acid, D-, L-, D, L-lactic acid, 6-hydroxyhexanoic acid, their cyclic derivatives such as glycolide (1,4-dioxane-2,5-dione), D-, L-dilactide (3,6-dimethyl-1,4-dioxane-2,5-dione), p-hydroxybenzoic acid and oligomers and polymers such as 3-polyhydroxybutyric acid, Polyhydroxyvaleric acid, polylactide (e.g.
  • the biodegradable polyether esters Q1 are characterized by a molecular weight (M n ) in the range from 5,000 to 100,000, preferably from 8,000 to 80,000, by a viscosity number in the range from 30 to 450, preferably from 50 to 400 g / ml (measured in o Dichlorobenzene / phenol (weight ratio 50/50) at a concentration of 0.5 wt .-% polyether ester Q1 at a temperature of 25 ° C), and a melting point in the range of 50 to 235, preferably from 60 to 235 ° C, and have both hydroxyl and carboxyl end groups, the molar ratio of carboxyl end groups to hydroxyl end groups being chosen to be greater than one, preferably greater than two.
  • M n molecular weight in the range from 5,000 to 100,000, preferably from 8,000 to 80,000
  • a viscosity number in the range from 30 to 450 preferably from 50 to 400 g / ml (
  • reaction of the polyether esters P1 with the hydroxycarboxylic acid B1 if desired in the presence of compound D is preferably carried out in the melt at temperatures in the range of 120 to 260 ° C under an inert gas atmosphere, if desired also under reduced pressure Print. You can do it discontinuously as well as continuously, for example in stirred tanks or (reaction) extruders, work.
  • reaction can be carried out by adding known per se Transesterification catalysts (see the above at Preparation of the polyether esters P1 described) accelerated become.
  • a preferred embodiment relates to polyetherester Q1 Block structures formed from components P1 and B1: when used Cyclic derivatives of B1 (Compounds IIb) can be used for the implementation with the biodegradable polyether ester P1 triggered by a so-called “ring-opening polymerization” through the end groups of P1, in a manner known per se, polyether esters Q1 can be obtained with block structures (to the "ring opening Polymerization "see Encycl. Of Polym. Science and Eng. Vol. 12, 2nd Ed., John Wiley & Sons, 1988, pp. 1 to 75, in particular Pp. 36 to 41).
  • the reaction can be carried out with addition conventional catalysts such as those already described above Carry out transesterification catalysts, particularly preferred is tin octanoate (see also Encycl. of Polym. Science and Closely. Vol. 12, 2nd Ed., John Wiley & Sons, 1988, pp. 1 to 75, in particular P.36 to 41).
  • Carry out transesterification catalysts particularly preferred is tin octanoate (see also Encycl. of Polym. Science and Closely. Vol. 12, 2nd Ed., John Wiley & Sons, 1988, pp. 1 to 75, in particular P.36 to 41).
  • the biodegradable polyether esters Q2 according to the invention are characterized by a molecular weight (M n ) in the range from 6000 to 80,000, preferably from 8,000 to 50,000, particularly preferably from 10,000 to 40,000 g / mol, by a viscosity number in the range from 30 to 450, preferably from 50 to 400 g / ml (measured in o-dichlorobenzene / phenol (weight ratio 50/50) at a concentration of 0.5% by weight of polyetherester Q2 at a temperature of 25 ° C.), and a melting point in the range from 50 to 200 ° C, preferably from 60 to 160 ° C, and have both hydroxyl and carboxyl end groups, the molar ratio of carboxyl end groups to hydroxyl end groups being chosen to be greater than one, preferably greater than two.
  • M n molecular weight in the range from 6000 to 80,000, preferably from 8,000 to 50,000, particularly preferably from 10,000 to 40,000
  • Particularly preferred bisoxazolines C1 are bisoxazolines of the general formula III
  • the bisoxazolines C1 of the general formula III are generally obtainable by the process from Angew. Chem. Int. Edit., Vol. 11 (1972), pp. 287-288.
  • bisoxazolines are 2,2'-bis (2-oxazoline), bis (2-oxazolinyl) methane, 1,2-bis (2-oxazolinyl) ethane, 1,3-bis (2-oxazolinyl) propane, 1 , 4-bis (2-oxazolinyl) butane, 1,4-bis (2-oxazolinyl) benzene, 1,2-bis (2-oxazolinyl) benzene and 1,3-bis (2-oxazolinyl) benzene.
  • the reaction of the polyether esters P1 with the bisoxazoline C1 takes place preferably in the melt (see also: J. Appl. Polym. Science, Vol. 33, pp. 3069-3079 (1987)), taking care is that if possible no side reactions occur that lead to a May cause crosslinking or gel formation.
  • the reaction is usually carried out at temperatures in the range from 120 to 260, preferably from 130 to 240, particularly preferably 140 to 220 ° C, with the addition of the bisoxazoline advantageous in several portions or continuously he follows.
  • the reaction of the polyether esters P1 with the bisoxazoline C1 even in the presence of common inert Solvents such as toluene, methyl ethyl ketone or dimethylformamide (“DMF”) or mixtures thereof, the reaction temperature usually in the range of 80 to 200, preferably from 90 to 150 ° C.
  • common inert Solvents such as toluene, methyl ethyl ketone or dimethylformamide (“DMF") or mixtures thereof
  • the reaction with the bisoxazoline C1 can be carried out batchwise or continuously, for example in stirred tanks, reaction extruders or be carried out via mixing heads.
  • the biodegradable polymers T1 according to the invention are characterized by a molecular weight (M n ) in the range from 10,000 to 100,000, preferably from 11,000 to 80,000, preferably from 11,000 to 50,000 g / mol, with a viscosity number in the range from 30 to 450, preferably from 50 up to 400 g / ml (measured in o-dichlorobenzene / phenol (weight ratio 50/50) at a concentration of 0.5% by weight of polymer T1 at a temperature of 25 ° C.) and a melting point in the range of 50 to 235, preferably from 60 to 235 ° C.
  • M n molecular weight
  • the polymer chains obtained preferably one Have block structure.
  • the implementation is usually analogous to the production of the Polyetherester Q2.
  • the biodegradable polymers T2 according to the invention are characterized by a molecular weight (M n ) in the range from 10,000 to 100,000, preferably from 11,000 to 80,000, particularly preferably from 11,000 to 50,000 g / mol, with a viscosity number in the range from 30 to 450, preferably from 50 to 400 g / ml (measured in o-dichlorobenzene / phenol (weight ratio 50/50) at a concentration of 0.5% by weight of polymer T2 at a temperature of 25 ° C.) and a melting point in the range from 50 to 235, preferably from 60 to 235 ° C.
  • M n molecular weight
  • the biodegradable polymers T3 according to the invention are characterized by a molecular weight (M n ) in the range from 10,000 to 100,000, preferably from 11,000 to 80,000 g / mol, a viscosity number in the range from 30 to 450, preferably from 50 to 400 g / ml (measured in o-dichlorobenzene / phenol (weight ratio 50/50) at a concentration of 0.5% by weight of polymer T3 at a temperature of 25 ° C.) and a melting point in the range from 50 to 235, preferably from 60 to 235 ° C.
  • M n molecular weight in the range from 10,000 to 100,000, preferably from 11,000 to 80,000 g / mol
  • a viscosity number in the range from 30 to 450 preferably from 50 to 400 g / ml (measured in o-dichlorobenzene / phenol (weight ratio 50/50) at a concentration of 0.5% by weight of polymer
  • the biodegradable polymers T3 are obtained by (g1) polyetherester P2, or (g2) a mixture consisting essentially of polyetherester P1 and 0.01 to 50, preferably 0.1 to 40% by weight, based on the polyether ester P1, hydroxycarboxylic acid B1, or (g3) a mixture consisting essentially of polyether esters P1 which have a different composition from one another 0.1 to 5, preferably from 0.2 to 4, particularly preferably from 0.3 to 2.5% by weight, based on the amount of the polyether esters, bisoxazoline C1 and with 0 to 5, preferably from 0 to 4 mol%, based on the respective molar amounts of component (a1), which were used to prepare the polyether esters (g1) to (g3) used, compound D, to react, wherein expediently carries out the reactions analogously to the preparation of the polyether esters Q2 from the polyether esters P1 and the bisoxazolines C1.
  • polyetherester P2 is used a, the recurring units of which are statistically distributed in the molecule are.
  • polyether esters P2 their polymer chains Have block structures.
  • Such polyether esters are P2 generally accessible by appropriate choice, in particular the molecular weight, the hydroxycarboxylic acid B1. So done after previous observations in general when using a high molecular weight hydroxycarboxylic acid B1, in particular with a p greater than 10, only an incomplete transesterification, for example even in the presence of the deactivators described above (see J. of Appl. Polym. Sc. Vol. 32, pp. 6191 to 6207, John Wiley & Sons, 1986, and Macrom. Chemistry, Vol. 136, pp. 311 to 313, 1970). If desired, the implementation can also be carried out in solution in the production of the polymers T1 from the polyether esters Carry out Q1 and the solvents named bisoxazolines C1.
  • high molecular weight hydroxycarboxylic acids B1 such as polycaprolactone or polylactide (e.g. EcoPLA®) or polyglycolide or polyhydroxyalkanoates such as 3-polyhydroxybutyric acid, polyhydroxyvaleric acid and mixtures thereof (e.g. Biopol®) with a molecular weight (M n ) in the range from 10,000 to 150,000 are used , preferably from 10000 to 100000 g / mol.
  • Another preferred embodiment relates to a blend obtainable by mixing from 99.5 to 40, preferably from 99.5 to 60% by weight of polyether ester P1 according to claim 1 or polyether ester Q2 according to claim 4 and from 0.5 to 60, preferably from 0.5 to 40% by weight of a high molecular weight hydroxycarboxylic acid B1, particularly preferably polylactide (eg EcoPLA®), polyglycolide, 3-polyhydroxybutyric acid, polyhydroxyvaleric acid and mixtures thereof (eg Biopol®), and polycaprolactone.
  • a high molecular weight hydroxycarboxylic acid B1 particularly preferably polylactide (eg EcoPLA®), polyglycolide, 3-polyhydroxybutyric acid, polyhydroxyvaleric acid and mixtures thereof (eg Biopol®), and polycaprolactone.
  • polylactide eg EcoPLA®
  • polyglycolide polyglycolide
  • 3-polyhydroxybutyric acid polyhydroxyvaleric acid and mixtures thereof
  • thermoplastic molding compositions T4 preferred in that short Complying with mixing times, for example when carrying out the Mixing in an extruder.
  • mixing parameters in particular the mixing time and, if desired, the use of Deactivators, molding compounds that are predominantly accessible Have blend structures, i.e. the mixing process is controlled in this way can be that at least partially transesterification reactions can take place.
  • O to 50, preferably O to 30 mol% of the adipic acid, or its ester-forming derivatives or mixtures thereof can be achieved by at least one other aliphatic C 4 -C 10 or cycloaliphatic C 5 -C 10 dicarboxylic acid or Dimer fatty acid such as succinic acid, glutaric acid, pimelic acid, suberic acid, azelaic acid or sebacic acid or an ester derivative such as its di-C 1 -C 6 alkyl ester or its anhydrides such as succinic anhydride, or mixtures thereof, replace, preferably succinic acid, succinic anhydride, sebacic acid and di-fatty acid C 1 -C 6 alkyl esters such as dimethyl, diethyl, di-n-propyl, diisobutyl, di-n-pentyl, dineopentyl, di-n-hexyl esters thereof, especially dimethyl succinic acid.
  • a particularly preferred embodiment relates to use as component (a1) in the mixture of succinic acid, adipic acid and glutaric acid described in EP-A 7445 and their C 1 -C 6 -alkyl esters such as dimethyl, diethyl, di-n-propyl, Diisobutyl, di-n-pentyl, dineopentyl, di-n-hexyl esters, especially their dimethyl esters and diisobutyl esters.
  • from 0 to 50, preferably from 0 to 40 mol% of the terephthalic acid or its ester-forming derivatives, or mixtures thereof, can be effected by at least one other aromatic dicarboxylic acid such as isophthalic acid, phthalic acid or 2,6-naphthalenedicarboxylic acid, preferably isophthalic acid Ester derivative such as a di-C 1 -C 6 alkyl ester such as dimethyl, diethyl, di-n-propyl, diisobutyl, di-n-pentyl, dineopentyl, di-n-hexyl ester, especially a dimethyl ester , or their mixtures.
  • aromatic dicarboxylic acid such as isophthalic acid, phthalic acid or 2,6-naphthalenedicarboxylic acid, preferably isophthalic acid Ester derivative such as a di-C 1 -C 6 alkyl ester such as dimethyl, diethyl, di-n-propy
  • the polymers according to the invention can be rolled, brushed, Apply spraying or pouring on coating substrates.
  • preferred Coating pads are those that are compostable are or rot like moldings made of paper, cellulose or Strength.
  • the polymers according to the invention can also be used for production of moldings are used that are compostable.
  • Shaped bodies are mentioned as examples: disposable items such as Dishes, cutlery, garbage bags, films for agriculture Early harvest, packaging films and containers for growing Plants.
  • the polymers according to the invention can be found in to spin itself in a known manner. You can thread if desired, stretch according to usual methods, draw twist, stretch bobbins, stretch warping, stretch finishing and stretch-. The stretching to so-called plain yarn can thereby in one and the same operation (fully drawn yarn or fully oriented yarn), or in a separate operation respectively. Stretch warping, stretch finishing and stretch texturing is generally carried out in a separate from spinning Working through.
  • the threads can be known in a conventional manner Process further into fibers. From the fibers are then Fabrics accessible by weaving, knitting or knitting.
  • the moldings, coating compositions and threads described above etc. can also contain fillers, if desired, which one during the polymerization process at any stage or subsequently, for example in a melt of the invention Can incorporate polymers.
  • fillers Based on the polymers according to the invention, from 0 to Add 80% by weight fillers.
  • Suitable fillers are, for example Carbon black, starch, lignin powder, cellulose fibers, natural fibers such as sisal and hemp, iron oxides, clay minerals, ores, Calcium carbonate, calcium sulfate, barium sulfate and titanium dioxide.
  • the Fillers can also contain stabilizers such as tocopherol (Vitamin E), organic phosphorus compounds, mono-, di- and Polyphenols, hydroquinones, diarylamines, thioethers, UV stabilizers, Nucleating agents such as talc and lubricants and mold release agents based on hydrocarbons, fatty alcohols, higher Carboxylic acids, metal salts of higher carboxylic acids such as calcium and Contain zinc stearate and montan waxes.
  • stabilizers etc. are in plastic manual, vol. 3/1, Carl Hanser Verlag, Kunststoff, 1992, pp. 24 to 28 described in detail.
  • the polymers according to the invention can also be added colored by organic or inorganic dyes as desired become.
  • the dyes can also be used in the broadest sense Filler.
  • a particular field of application of the polymers according to the invention relates to the use as a compostable film or compostable coating as the outer layer of diapers.
  • the The outer layer of the diapers effectively prevents the passage of Liquids inside the diaper from fluff and superabsorbents preferably of biodegradable superabsorbents, for example based on cross-linked polyacrylic acid or cross-linked Polyacrylamide.
  • As the inner layer of the diaper can to use a nonwoven fabric made of a cellulose material.
  • the outer layer of the diapers described is biodegradable and thus compostable. It disintegrates when composting, so that entire diaper rots while having an outer layer of for example Polyethylene-coated diapers are not without first Shredding or elaborate separation of the polyethylene film can be composted.
  • polymers according to the invention and molding compounds relate to the production of adhesives in known manner (see for example Encycl. of Polym. Sc. and eng. Vol.1, "Adhesive Compositions", pp. 547 to 577).
  • Analogous the polymers according to the invention can be used to teach EP-A 21 042 and molding compositions also with suitable tackifying thermoplastic Resins, preferably natural resins, as described there Process methods.
  • Analogous to the teaching of DE-A 4,234,305 the polymers and molding compositions according to the invention can also be added Process solvent-free adhesive systems such as hot-melt films.
  • thermoplastic starch as described in WO 90/05161
  • Molding compounds can be based on previous observations their hydrophobic nature, their mechanical properties, their complete biodegradability, their good compatibility with thermoplastic starch and not least because of its cheap Advantageously use the raw material base as a synthetic blend component.
  • polymers according to the invention in agricultural mulch, Packing material for seeds and nutrients, substrate in Adhesive films, baby panties, bags, sheets, bottles, boxes, Dust bags, labels, pillowcases, protective clothing, hygiene items, Handkerchiefs, toys and wipers.
  • polymers and Molding compounds relate to the production of foams, whereby one generally works according to methods known per se (see EP-A 372,846; Handbook of Polymeric foams and Foam Technology, Hanser Publisher, Kunststoff, 1991, pp. 375 to 408).
  • the polymer or molding composition according to the invention is initially melted, if desired with addition of up to 5% by weight Compound D, preferably pyromellitic dianhydride and trimellitic anhydride, then mixed with a blowing agent and the like the mixture obtained is subjected to reduced pressure by extrusion, whereby the foaming arises.
  • Compound D preferably pyromellitic dianhydride and trimellitic anhydride
  • biodegradable polymers in a cheap raw material base with readily available starting materials such as adipic acid, terephthalic acid and common diols, in interesting mechanical properties by combining "hard” (through the aromatic Dicarboxylic acids such as terephthalic acid) and “soft” (by the aliphatic dicarboxylic acids, such as Adipic acid) segments in the polymer chain and the variation of the Applications through simple modifications, with good degradation behavior through microorganisms, especially in compost and in Soil, and in some resistance to microorganisms in aqueous systems at room temperature, which for many applications is particularly advantageous.
  • the aromatic dicarboxylic acids of components (a1) in biological attack is made possible for various polymers and thus achieves the desired biodegradability.
  • polymers can advantageously be used with predominantly statistically distributed monomer blocks, Polymers with predominantly block structures as well as polymers with predominantly Blend structure or blends can be obtained.
  • the polymers were cooled in a mill with liquid nitrogen or dry ice and finely ground (the larger the surface of the ground material, the faster the enzymatic breakdown).
  • 30 mg of finely ground polymer powder and 2 ml of a 20 mmol aqueous K 2 HPO 4 / KH 2 PO 4 buffer solution (pH value: 7.0) were placed in an Eppendorf reagent tube (2 ml) and 3 h equilibrated on a swivel at 37 ° C. Then 100 units of lipase from either Rhizopus arrhizus, Rhizopus delemar or Pseudomonas pl.
  • a DOC measurement was carried out only with buffer and enzyme (as enzyme control) and one only with buffer and sample (as blank value).
  • the determined ⁇ DOC values can be used as a measure of the enzymatic Degradability of the samples can be considered. They are each in Comparison to a measurement with powder from Polycaprolacton® Tone P 787 (Union Carbide). When evaluating is on it to make sure that it is not absolutely quantifiable data is. On the relationship between the surface of the grist and speed of enzymatic degradation was discussed above already pointed out. Furthermore, the enzyme activities vary.
  • the molecular weights were measured by means of gel permeation chromatography (GPC): stationary phase 5 MIXED B polystyrene gel columns (7.5x300 mm, PL-gel 10 ⁇ ) from Polymer Laboratories; Temperature control: 35 ° C. mobile phase Tetrahydrofuran (flow: 1.2 ml / min) calibration Molecular weight 500-10000000 g / mol with PS calibration kit from Polymer Laboratories.
  • GPC gel permeation chromatography
  • ethylbenzene / 1,3-diphenylbutane / 1,3,5-triphenylhexane / 1,3,5,7-tetraphenyloctane / 1,3,5,7,9-pentaphenyl decane detection RI (Refractive Index) Waters 410 UV (at 254 nm) Spectra Physics 100
  • the DSC measurements were made with a DSC 912 + Thermal Analyzer 990 by DuPont. The temperature and enthalpy calibration was done in the usual way. The sample weight was typically 13 mg. Heating and cooling rates were - except when otherwise noted - 20 K / min. The samples were among the following Measure conditions: 1. Heating up of samples in the delivery state, 2. Rapid cooling from the melt, 3. Heating up Run on samples cooled from the melt (samples from 2). The second DSC runs were used after memorization a uniform thermal history, a comparison between different samples.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Public Health (AREA)
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  • Veterinary Medicine (AREA)
  • General Chemical & Material Sciences (AREA)
  • Polyesters Or Polycarbonates (AREA)
  • Biological Depolymerization Polymers (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
EP96902980A 1995-02-16 1996-02-03 Biologisch abbaubare polymere, verfahren zu deren herstellung sowie deren verwendung zur herstellung bioabbaubarer formkörper Expired - Lifetime EP0809666B2 (de)

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DE1995105185 DE19505185A1 (de) 1995-02-16 1995-02-16 Biologisch abbaubare Polymere, Verfahren zu deren Herstellung sowie deren Verwendung zur Herstellung bioabbaubarer Formkörper
PCT/EP1996/000458 WO1996025448A1 (de) 1995-02-16 1996-02-03 Biologisch abbaubare polymere, verfahren zu deren herstellung sowie deren verwendung zur herstellung bioabbaubarer formkörper

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JPH11500157A (ja) 1999-01-06
EP0809666A1 (de) 1997-12-03
EP0809666B1 (de) 1998-10-21
EP0809664B1 (de) 2000-05-17
EP0809664A1 (de) 1997-12-03
DK0809664T3 (da) 2000-08-28
DE19505186A1 (de) 1996-10-31
DE19505185A1 (de) 1996-10-24
US5889135A (en) 1999-03-30
DE59605251D1 (de) 2000-06-21
JP3471810B2 (ja) 2003-12-02
ES2147918T3 (es) 2000-10-01
WO1996025446A1 (de) 1996-08-22
WO1996025448A1 (de) 1996-08-22
KR19980702244A (ko) 1998-07-15

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